JPH02188584A - Novel heterocyclic compound, production thereof and pigment-dye composition containing the same - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 and R2 represent H or methyl; X represents -N(R3)R4 (R3 and R4 represent H or methyl)]. USE:A pigment or dye, which exhibits a color tone of stable and high chroma. PREPARATION:A resorcinol derivative expressed by formula II (R5 and R6 represent H, halogen, 1-20C alkyl, alkoxy or hydroxy alkyl) (preferably resorcinol, 4-chlororesorcinol, etc.) is reacted with a pyrimidine derivative (preferably 2,4,5,6-tetraaminopyridine, etc.) expressed by formula III (R7 to R10 represent H, 1-20C alkyl, hydroxyalkyl, aralkyl, aminoalkyl, alkylaminoalkyl, aryl, thiol or formula IV), etc., to afford a compound expressed by formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel heterocyclic compound, a method for producing the same, and a pigment/dye composition containing the same.

[Problems to be solved by conventional technology and invention]

Conventionally, nitro and diazo aromatic compounds have been widely used as pigments and staining agents. Compared to these compounds, a compound with higher color shading and stability has been developed using the following formula (where Y represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, or an alkyl group, and 2 represents an oxygen atom or a sulfur atom). or an amino group, Qt! indicates an oxygen atom or an amino group, and indicates that this ring is an aromatic ring or alicyclic ring which may further have a substituent] From a rigid closed ring structure represented by Naru phenazine,
Heterocyclic compounds such as fenoxacin and phenothiazone are known, and these compounds are used as functional dyes such as various indicators, laser dyes, and coloring agents.

However, these compounds have not yet been fully satisfactory in terms of stability, color saturation, and fastness. Therefore,
There has been a desire for compounds that can be used as more stable and highly chromatic dyes and pigments.

[Means to solve the problem]

In view of this situation, the present inventors have conducted studies to solve the above problems, and have developed a bicyclic heterocyclic compound into which a birimicin ring is introduced.

The present invention was completed based on the discovery that compositions that exhibit stable and highly saturated color tones are useful as pigments and dyes, and that these compounds include novel compounds.

That is, the present invention is based on the following general formula (N'')R11R? ＼　／ R.

[In the formula, s I'Ls and R6 are the same or different and represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyalkyl group, and s R7 and Rs are, The same or different hydrogen atoms or linear or branched alkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups, 1 aralkyl group, aminoalkyl group, alkylaminoalkyl group or aryl group, or adjacent nitrogen atoms. Together they form a piperidino group, a morpholino group or an azilkylidenimino group, and X, depending on the group, represents a hydrogen atom or a linear or branched alkyl group, hydroxyalkyl group, aminoalkyl group or alkylaminoalkyl group or together with adjacent nitrogen atoms to form a piperidino group or a morpholino group 6), a thiol group or a compound of the formula Rs R7\/S (wherein Rs%"@%R? and R, are as defined above) The present invention provides a pigment/dye composition containing a heterocyclic compound represented by the following, and a method for producing a compound of general formula (IV).

The present invention also provides a heterocyclic compound represented by the following general formula (summer): [wherein R1 and R are the same or different (here, R3 and R4 are the same or different and represent a hydrogen atom or a methyl group] It provides:

The compound of general formula (ff) of the present invention is produced, for example, according to the following reaction formula.

(Ten) (I) [s in the formula
R11s ite, R? , Rs %R1I , Rto
and X are the same as above] That is, the heterocyclic compound (ff) of the present invention is produced by reacting the xylicin derivative (I) and the pyrimicin derivative (I) in the presence of an oxidizing agent.

Preferred specific examples of the xylysine derivative represented by the general formula (I) include resorcinol, 4-chlorresorcinol, 1
, 2.4-benzenetriol, 2.6-zohydroxyethylbenzene 7. 2.4-dihydroxyethylbenzene, 3.5-dihydroxyethylbenzene% 26-dihydroxyzolobylbenzene, 2.4-dihydroxychlorobenzene, 3.5 -dihydroxyzorobylbenzene,
2.6-zohydroxyisoderobylbenzene, 2.4-
Zohydroxyisoderobylbenzene, 3.5-zohydroxyisoderobylbenzene% 26-dihydroxybutylbenzene, 2.4-dihydroxybutylbenzene, 3
．． 5-dihydroxybutylbenzene, 2,4-dimethyl-1,3-zohydroxybenzene, 2,4-diethyl-
1,3-zohydroxybenzene, 2,4-diisopropyl-1,3-dihydroxybenzene, 2,4-dibutyl-1,3-zohydroxybenzene, 2,3-dimethyl-
1,5-zohydroxybenzene, 2,3-zoethyl-1
, 5-dihydroxybenzene, 2,3-zoderopyru-1
．． 5-zohydroxybenzene, 2,4-dimethyl-1,
5-zohydroxybenzene, 2,4-diethyl-1,5
-zohydroxybenzene, 2,4-sibutyl-1,5-
Dihydroxybenzene, 2.5-dimethyl-1,3-zohydroxybenzene/, 2.5-zoethyl-1,3-zohydroxybenzene, 2.5-zoinderovir-1,3-
Examples include dihydroxybenzene, 2,5-sibutyl-1,3-dihydroxybenzene, and the like. Of these, resorcinol, 4-chlorresorcinol, monomethyl-m-dihydroxybenzene, and dimethyl-m-dihydroxybenzene are particularly preferred. These compounds (I) are known in the literature and can be produced by methods known per se.

Preferred specific examples of the birimicin derivative represented by the general formula (I) include 2,4,5.6-teto-2-amino birimicin, 4,5-cyamino-2,6-bismethylaminopyrimicin, 2. 5-cyamino-4,6-bismethylaminobilimicin, 4.5-cyamino-6-butylamino-2-dimethylaminobilimicin, 4.5-cyamino-
6-diethylamino-2-zomethylaminovirimizone,
4,5-cyamino-2-diethylamine-6-methylaminopyrimidine, 4,5-cyamino-2-methylamino-6-nithylaminopyrimizo/, 4,5-cyamino-
2-dimethylamino-6-iso10pyraminovirimicin, 4.5-methylamino-2-methylaminovirimicin, 4.5-cyamino-2-dimethylamino-6-olovylaminovirimizone, 2, 4.5-triamino-6-
Dimethylamino-bilimidine, 4,5.6-triamino-2-dimethylaminobilimicin, 2.4.5-)riamino-6-methylaminobilimicin, 4,5.6-triamino-2-methylaminobilimicin , 4.5-cyamino-2-dimethylamino-6-biperizonovirimizone%
4.5-cyamino-6-methylamino-2-piberisonobilimizone, 2,4.5-triamino-6-anilitupyrimizone, 2,4.5-triamino-6-pencylaminobilimicin , 2,4.5-triamino-6-penzolidenaminovirimizone, 4,5.6-)riamino-
2-piperidinovirimidine, 2,4,6-dorismetelamin-5-7 minobirimicin, 2. ．． 45-triamino-6-zone n-propylaminopyrimidine, 2,4.
5-) Liamino-6 monomorpholinovirimizone, 2,5.
6-) riamino-4-dimethylaminopyrimidine, 4.
5.6-triamino-2-morpholinopyrimidine, 2,
4.5-triamino-6-β-hydroxyethylaminobilimicin, 4.516-triamino-2-β-amino-ethylaminopyrimidine, 2,5.6-triamino-
4-β-methylamino-ethylaminobilimicin, 2.
5-cyamino-4,6-pis-T-zoethylaminoprobylamino♂limizone, 4,5-cyamino-2-methylamino-6-β-hydroxyethylaminopyrimidine, 5-amino-2,4,6- Doriethylaminovirimicin, 2,4-bis-β-hydroxyethylamino-6-
Anilino-5-aminobilimicin, 4,5.6-triamino-2(IH) birimycinthion, 4,5-cyamino-6-cymetelamin-2(IM) birimicinthione,
5-amino-4,6-bismethylamino-2(IH) birimycinthione, 4.5-bisethylamino-6-butylamino-2(IH) birimycinthioy% 4.5-cyamino-6-diethylamino- 2(IH)1:″limizonthione, 4.5-cyamino-6-me(IH) birimisinthione, 4.5-cyamino-6-210 bilamino-
2(I11) Virimisynthione, 4,5-cyamino-6
- ituderobylamino-2 (IH) virimi scinthione,
4.5-cyamino-6-dimethylamino-2(IH) virimicinthione, 4.5-cyamino-6-biperizono 2(IH) virimicinthio/, 4.5-cyamino-6-
Aniritu 2 (IH) virimizo/thione, 4゜5-cyamino-6-pencylamino-2 (IH) virimizo/thione, 4.5-cyamino-6-penzolidenamino 2 (
IH) Virimi scinthione, 4,5-cyamino-6-zone n-propylamino-2 (IH) Virimi scinthione, 4
．． 5-Cyamino-6・-morpholino-2(IH) birimycinthione, 4-dimethylamino-5,6-diamino-
2(IH) Virimisynthion% 4.5-cyamino-6-
β-Hydroxyethylamino-2(IH) birimycinthion, 5,6-zoamino-4-β-methylaminoethylamino-2(IH) birimycinthion, 5-amino-4
,6-pis-γ-zoethylaminoderobyl amino-2
(IH) Virimi scinthione, 5-amino-4,6-diethylamino-2 (IH) Virimi scinthione, 4-bis-
Examples include β-hydroxyethylamino-6-anilino-5-amino-2 (IK) birimisinthione. These compounds (m) are inorganic acids, carboxylic acids containing a linear or branched alkyl group having 1 to 20 carbon atoms, mono- or ? Organic acids such as hydroxycarboxylic acids or sulfonic acids, such as hydrochloric acid, phosphoric acid.

It may also be used in the form of a salt with acetic acid, zolopionic acid, lactic acid, citric acid, etc.

Virimicin derivatives (I) are also known in the literature and can be produced by methods known per se.

Examples of the oxidizing agent used include hydrogen peroxide, peracid, potassium ferricyanide, and the like. As the peracid, an alkali metal persulfate-ammonium persulfate or the like is used.

The reaction is preferably carried out, for example, in an aqueous alkaline medium at a temperature of -5 DEG to 40 DEG C. As an aqueous alkaline medium,
Aqueous solutions of sodium hydroxide, potassium hydroxide, ammonia and the like are preferred, and may contain organic solvents such as alcohol and acetone.

The heterocyclic compound (b) of the present invention thus obtained is stable, has a high molecular extinction coefficient, and has an extremely narrow spectral width, so it can be applied to pigments and dyes as a highly saturated red pigment.

When the compound (Iv) of the present invention is used as a pigment/dye composition, Fi
The compound (IT) of the present invention may be mixed with commonly used supporting materials and auxiliary agents.

Such supporting substances include extender pigments such as titanium oxide, zinc oxide, calcium carbonate, and talc; varnishes, phenolic resins, vinyl chloride resins, acrylic resins, etc. Examples include natural and synthetic resins such as polyester resin, polystyrene, and polyethylene.

In addition, the auxiliary agents include a surfactant having pigment dispersion ability and emulsification ability; a gloss imparting agent consisting of higher fatty acids, ester oil, silicone and its derivatives; a sequestering agent (pH 14);
Examples include conditioning agents, buffering agents, and the like.

In addition, pigments of the present invention containing these supporting substances, auxiliary agents, etc.
Other pigments and dyes may be further added to the dye composition for the purpose of color toning and the like.

The pigment/dye composition of the present invention contains a heterocyclic compound (I)
eo, 1 to 50% by weight is preferably blended.

[Action and effect of the invention]

The heterocyclic compound (ff) #'i of the present invention is stable and has various red tones, has a high molecular extinction coefficient, and has an extremely narrow spectral width, so the color tone No. 7 has high saturation. Pigment/dye compositions containing this pigment exhibit high fastness over a wide pH range and are useful as highly saturated and stable colorants.

〔Example〕

Next, the present invention will be explained with reference to Examples.

In the examples below, absorption spectra of sample solutions and reflection spectra of sample solids are shown. Among them, λma indicates the wavelength showing maximum absorption, and ΔλBl/! indicates the spectral width of the part where the absorbance shows the number λ-E (width to the long wavelength side (see Figure 1)). Note that colors such as #1 where this ΔλB'/2 is small indicate high saturation. .

Example 1 0.1 mol of 2.4,5.6-teto2aminopyrimidine and 0.1 mol of 2-methylresorcin were mixed at pH 9.5.
was dissolved in an aqueous solution of Na1CO1. Then 0.4 mol of potassium ferricyanide dissolved in a small amount of water is gradually added to this solution with stirring. After the addition was completed, the reaction mixture was allowed to stand, then neutralized with 2N sulfuric acid, and the resulting precipitate was washed with water.
Dry. In this way, the crude target compound [formula (I)
In, R1=CH3, R,=R3=R4==H,
It was recrystallized from a water mixture and purified once.

M8:M”243.0757 (Calc, 243.07
56) Molecular formula CIIHIIN! To! 1sC-NMR: Figure 2 XR spectrum Figure 3 Visible absorption spectrum λ in ethanol solution:
492 nm m & 0.1 mol of Limizone and 0.1 mol of 2-methylresorcin,
The target compound [R1 in formula (I)
=CH5, R1=R3=R4=n, X=N(CHs
h) About 0.075 mol of dimethyl sulfoxide was obtained.
It was purified by recrystallization from a water mixture.

MS2M+271 Molecular formula ctsHtsl'Jso Snow 13C-NMR: Figure 4 IR spectrum: Figure 5 Visible reflection spectrum of dry dye λ: 535 am ax ΔλB5'2 near 4am Color tone Reddish-purple Example 3 2.4,5.6-Chitra 0.1 mol of aminopyrimicin and 0.1 mol of resorcin were added to N&ICO3 at pH 9.5.
Dissolved in an aqueous solution and reacted in the same manner as in Example 1, R1=R1=R3=R4=H,
=NH snow] was obtained and purified by recrystallization from a dimethyl sulfoxide-water mixture.

M8:M"229 Molecular formula 010H7NlIO! Visible reflection spectrum of dry dye λ: 510 nm ax JJB'/2: 82 am Color tone Reddish brown Example 4 2-dimethylamino-4,5,6-driamifunobirimizone 0.1 mol and 0.1 mol of Resolcif, pH 9,
5ONalCO1 aqueous solution and reacted in the same manner as in Example 1 to obtain the target compound [s R1= in formula (I)]
Rx= Rs= R4= He X= N(CHsh
) about 0.07 mol was purified by recrystallization from a mixture of dimethyl sulfoxide and water.

MS: M”2 s 7 Molecular formula ct)tttNso* Visible reflection spectrum of dry dye λ: 530 nm aw ΔλB/2.61 Dark tone Purple red Example 5 4.5.ff-) Riamino-2(I)f ) Dissolve 0.1 mol of girimisinthione and 0.1 mol of 2-methyl resorcif in a 1N aqueous sodium hydroxide solution, then gradually add 0.2 mol of potassium ferricyanide dissolved in a small amount of water to this solution with stirring. After the addition was completed, the reaction mixture was left to stand, and then neutralized with 2N sulfur, and the resulting precipitate was washed with water and dried.In this way, a mixture of the desired monosulfide and the disulfide-bonded dimerized compound of the oxidant was obtained. About 0.07 mol (in terms of 2-methylresorcin) of Formula 0)% Formula % Mixture of Ruphid Forms] was obtained.

Visible reflection spectrum λ of dry pigment: 514 zlm mlK! ΔλB, /2: 70 nm Color Tone Crimson Example 6 4.5.6-) 0.1 mole of lyamino-2(IH)pyrimiscinthione and 0.1 mole of resorcin were 1N hydroxide) IJium aqueous solution and reacted in the same manner as in Example 5 to obtain a mixture of the target monosulfide and the oxidized dimerized compound having disulfide bonds [in formula (I), R
1=Visible reflection spectrum of dry dye λ: 51 gnmax Δλ'/"60+ub B 2. Color tone Red Example 7 4.5.6-) 0.1 mol of riamino-2(IH) virimisontheone and 0.1 mol of sa-chlororesorcin. 1 mole to 1N
was dissolved in an aqueous sodium hydroxide solution and reacted in the same manner as in Example 5 to form a mixture of disulfide-bonded 2tL compound of the desired monosulfide and oxidant [formula (I
) % Formula % Mixture of Ruphid Forms] Approximately 0.07 mol (4-chlororesorcinol) i.

Visible reflectance spectrum of dry dye λ: 526nm mllll! Δλ8shi', :(i4nm Color tone: crimson

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a method for measuring ΔλBt/2. Figure 2
and Figure 3 shows the 13C-N of the compound obtained in Example 1.
2 is a drawing showing MR and ZR spectra, respectively. 4 and 5 show the 13C of the compound obtained in Example 2.
-NMR? Call! 3A and 3B are drawings each showing an R spectrum. That's all), Snake: and;

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_2 are the same or different and represent a hydrogen atom or a methyl group, and X is A heterocyclic compound represented by the group -N (where R_3 and R_4 are the same or different and represent a hydrogen atom or a methyl group). 2. In the presence of an oxidizing agent, the following general formula (II) ▲ Numerical formula, chemical formula, table etc.▼(II) [In the formula, R_5 and R_6 are the same or different and represent a hydrogen atom, a halogen atom, or a straight or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyalkyl group] Resorcinol derivatives represented by the following general formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) Straight chain or branched alkyl group, hydroxyalkyl group,
represents an aralkyl group, an aminoalkyl group, an alkylaminoalkyl group or an aryl group, or together with adjacent nitrogen atoms forms a piperidino group, a morpholino group or an aralkylidenimino group, and X is a group ▲ of the formula
There are chemical formulas, tables, etc. ▼ (Here, R_1_1 and R
_1_2 are the same or different and represent a hydrogen atom or a linear or branched alkyl group, hydroxyalkyl group, aminoalkyl group or alkylaminoalkyl group, or together with adjacent nitrogen atoms represent a piperidino group or a morpholino group. ), thiol group or formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R_5, R_6, R_7 and R_8 are the same as above) represents a group] of a heterocyclic compound represented by the general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [In the formula, R_5, R_6, R_7, R_8 and X are the same as above] Manufacturing method. 3. The following general formula (IV) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IV) [In the formula, R_5 and R_6 are the same or different and are hydrogen atoms, halogen atoms, or A branched alkyl group, an alkoxy group, or a hydroxyalkyl group, and R_7 and R_8 are the same or different hydrogen atoms or a straight or branched alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, an aralkyl group, an amino represents an alkyl group, an alkylaminoalkyl group, or an aryl group, or together with an adjacent nitrogen atom, forms a piperidino group, a morpholino group, or an aralkylidenimino group, and X is a group ▲ mathematical formula, chemical formula, table, etc. There is ▼ (here R_1_1
and R_1_2 are the same or different and represent a hydrogen atom or a linear or branched alkyl group, hydroxyalkyl group, aminoalkyl group, or alkylaminoalkyl group, or together with adjacent nitrogen atoms, represent a piperidino group or a morpholino group. ), a thiol group or a heterocyclic compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R_5, R_6, R_7 and R_8 are the same as above) A pigment/dye composition characterized by containing.